London Treaty has been entered according to the trend of protection of environment of the earth, and dumping waste photographic processing liquids into ocean has been substantially prohibited. Accordingly, efforts to reduce the photographic waste liquids have been made in the field of photography. Regarding the fixing solution, reduction of the waste liquid and that of the replenishing amount have been studied as shown in Japanese Patent Publication Open to Public Inspection (JP O.P.I.) no. 8-201997.
Besides, increasing in the sensitivity of color film has been progressed accompanied with a prompt growth of demand for a film with lens and spread of a camera with a zoom function. Such the high speed film usually has a high silver iodide content and coated silver amount. As a result of that, the load on the treating process, particularly on the bleaching process, has become a problem.
Furthermore, an ammonium salt such as ammonium thiosulfate and ammonium thiocyanate is used as a fixing agent to be used in the fixing solution from the viewpoint of a clearing time. However, degradation of working environment has been made since such the ammonium slat forms ammonia gas when the pH of the fixing solution is exceeded to 7, and the ammonia gas drifts around the automatic processor and causes displeasure order. Particularly, the problem is made serious if the automatic processor is installed in a badly ventilated place such as a foods store in a basement of a building. The fixing tends to made insufficient when a receipt in which the amount of ammonium salt is reduced as small as possible is applied as a countermeasure of such the problem.
Moreover, the fixing solution is with circulation in the treating tang of the automatic processor for purposes of uniforming the temperature, removing dust in the tank and stirring the solution. However, contact of the fixing solution with air is accelerated by the circulation and the fixing solution tends to be oxidized. The oxidation of the fixing solution causes formation of sulfurized substance and a serious problem is raised when the sulfurized substance is adhered to the light-sensitive material. Such the problem is made more serious when the replenishing amount is reduced. An insufficient fixation is caused when the circulation is reduced as a countermeasure to such the problem.
In the silver removing process in which silver halide and metallic silver in the light-sensitive material is removed into a processing solution, silver halide tends to be remained in the light-sensitive material in a form of unfixed silver which causes insufficient fixation. Such the insufficient fixation is caused by raising the accumulated silver amount in the processing solution caused by reduction of the replenishing amount or processing a light sensitive material having a high coated silver amount, the use of a fixing solution having a reduced ammonium ion content, and the use of an automatic processor with reduced circulation.
When the insufficient fixation is formed in a color light-sensitive material, a color remaining stain is formed since a dye is remained accompanied with a lot of silver remaining in the light-sensitive material. A serious problem such as change in the tone of the light-sensitive material and degradation in the image quality is raised at the print of image when such the color stain is formed. It is usual in a mini-lab that various level of conditions (channels) suited for various light-sensitive materials are previously set using a standard negative film and the printing of a kind of film is performed by using the channel suited to such the film. For such the procedure, it is necessary that the negative is constantly finished. Accordingly, color prints having a constant quality cannot be obtained when the color stain is formed since the density of the negative is varied. The insufficient fixation usually tends to be formed ununiformly. In such the case, the quality of print is considerably degraded.
On the other hand, a method is disclosed in JP O.P.I. No. 8-29930 in which the majority of coated silver is remained in the part of undeveloped part other than image formed part of a monochromatic light-sensitive material. In the monochromatic light-sensitive material, however, such the problem is not made serious since the problem of the color stain and that prints having a constant quality is prepared by a printer are hardly raised in the monochromatic light-sensitive material.
It is difficult to solve the above-mentioned problems regarding the fixing process of color light-sensitive material since in the color light-sensitive material, the reduction of replenishing of the fixing process, the reduction of the ratio of ammonium ion and the reduction of the circulation in an automatic processor are difficult because it is necessary to perfectly remove the silver hailed from the light-sensitive material from the viewpoint of the color stain.
Recently, a high-speed color negative film having a high amount of coated silver is frequently used, and the replenishing in the fixing process is reduced. Therefore, silver halide tends to be remained in a form of unfixed silver in the light-sensitive material and tend to cause an insufficient fixation. A large amount of silver halide is remained in the light-sensitive material when the insufficient fixation is occurred, and the silver salt is changed to black silver by heat, moisture of light, or the silver halide is reacted by thiosulfate remained in the light-sensitive material to form silver sulfide after the processing. When the black silver or silver sulfide is formed in a negative film, problems such as change in the tone of the light-sensitive material and degradation in the image quality are raised after storage, and serious problems are caused at the printing of the image in the future.
Moreover, a demand of reducing replenishing amount is also raised in the processing of a color paper, and an insufficient fixation tends to be occurred when the replenishing is reduced, and the degradation of storage ability image is feared.
As above-mentioned, it has been common knowledge that silver halide in light-sensitive material is completely removed for reducing the replenishment in the fixing process. Besides, the storage ability of image can be improved by the invention in which unfixed silver is stabilized by the use of specific compound and silver salt is positively remained in the light-sensitive material.
On the other hand, a method is disclosed in JP O.P.I. No. 8-29930 in which the majority of coated silver is remained in the part of undeveloped part other than image formed part of a monochromatic light-sensitive material. However, the problem of the storage ability of dye image at the image forming portion of color light-sensitive material is not raised since the image is formed by silver, not dye, in the monochromatic light-sensitive material. Accordingly, the problem to be solved in this publication is quite different from the invention, and there is no description suggesting the invention in the publication.
The above-mentioned insufficient fixation of negative film tends to be unevenly formed on the film, and a serious problem is raised since the unevenness on the negative is printed on the color paper when the negative is printed on the paper. It has been found by the inventors that a suitable print can he obtained, even when the silver salt is remained in the light-sensitive material, by removing the influence of the silver salt on the transmitting light by the use of the compound of the invention. The problem of the unevenness insufficient fixation also can be soled.